JP6279588B2 - Polybenzoxazine composition - Google Patents

Description

Detailed Description of the Invention

[Field of the Invention]
A process for preparing poly (benzoxazine) will be described.

[background]
Benzoxazines and compositions containing benzoxazines are known (eg, US Pat. Nos. 5,543,516 and 6,207,786 (Ishida et al.), S. Rimdusit and H. Ishida, “ Development of New Class of Electronic Packaging Materials Based on Ternary Systems of Benzoxazine, Epoxy, and Phenolic Resins ", Polymer, 41,7941~49 (2000), as well as H.Kimura et al.," New Thermosetting Resin from Bisphenol a-based Benzoxazine and Bisazozolein ", J. App.P lym.Sci., 72,1551~58 (1999) see.)

  US Pat. No. 7,517,925 (Derschem et al.) Describes benzoxazine compounds and thermosetting resin compositions prepared therefrom. This composition is said to be useful for increasing adhesion at interfaces within microelectronic packages, reducing shrinkage upon curing, and reducing the coefficient of thermal expansion (CTE).

  U.S. Pat. No. 7,053,138 (Magendie et al.) Describes a composition comprising benzoxazine and a thermoplastic or thermosetting resin in the manufacture of prepregs and laminates. It is said that a flameproof laminated resin having a high glass transition temperature can be obtained from this composition.

  US Pat. No. 6,376,080 (Galo) heats a molding composition comprising benzoxazine and a heterocyclic dicarboxylic acid to a temperature sufficient to cure the molding composition to form a polybenzoxazine. A method for preparing polybenzoxazine is described. This composition is said to have almost zero volume change after curing.

  US Pat. No. 6,207,586 (Ishida et al.) States that polymerization of a benzoxazine monomer into a polymer is an ionic ring-opening polymerization that converts the oxazine ring to another structure, such as a linear polymer or larger heterocycle. It is described that it is considered to be. The chain transfer process is believed to limit the molecular weight of the resulting polymer, resulting in some branching. FTIR (Fourier Transform Infrared) analysis is often used to monitor the conversion of the oxazine ring to a polymer and estimate the polymerization rate at different temperatures. NMR (nuclear magnetic resonance) spectroscopy can also be used to monitor the conversion of benzoxazine monomer to polymer.

  Epoxy adhesives are widely used in structural adhesive applications and are suitable for many demanding industrial applications. However, epoxies have many significant drawbacks that limit their use, including limited high temperature stability, high hygroscopicity, shrinkage, and large exotherm during polymerization.

  In order to overcome many of the limitations in epoxies, polybenzoxazines have been proposed. Polybenzoxazines generate less heat upon curing, have less shrinkage, have higher thermal stability, have fewer byproducts, and can be easily prepared from benzoxazines, whereby benzoxazines It is easily prepared from amines, formaldehyde, and phenols in high yield. However, current methods of preparing polybenzoxazines require relatively high temperatures, typically resulting in brittle and highly crosslinked polymers.

  Attempts to lower the polymerization temperature included the addition of various phenol or Lewis acid promoters, or the copolymerization of benzoxazine with other monomers such as epoxides or phenol-formaldehyde. However, the resulting polybenzoxazine-epoxy hybrid continues to retain many of the limitations of epoxy and has lost many desirable features such as epoxy toughness.

[Overview]
The present disclosure is directed to a polymerizable composition comprising a benzoxazine compound and a catalyst selected from elemental sulfur, elemental selenium, and a sulfide or selenide of a Group V element or Group VI element. The polymerizable composition can be cured (polymerized) to produce a cured composition useful in coatings, sealants, adhesives, and many other applications. The present disclosure further provides a polymerizable composition comprising a benzoxazine compound and a catalyst, which when polymerized is useful in high temperature structural adhesive applications. The present disclosure further provides a method of preparing a polybenzoxazine comprising heating the polymerizable composition at a temperature and time sufficient to effect polymerization. In some embodiments, a film-forming agent that can be non-reactive or reactive with benzoxazine may be added to the polymerizable composition.

  The present disclosure overcomes many of the well-known disadvantages in polybenzoxazine polymerization, such as lower polymerization temperatures and reduced exotherm. In some embodiments, the product polybenzoxazine is a flexible solid with excellent thermal stability and is useful for many industrial applications.

  As used herein, the term “benzoxazine” includes compounds and polymers having a characteristic benzoxazine ring. In the exemplified benzoxazine groups, R is a mono- or polyamine residue.

  As used herein, “alkyl” includes linear, branched, and cyclic alkyl groups, including both unsubstituted and substituted alkyl groups. Unless otherwise specified, alkyl groups typically contain 1-20 carbon atoms. Examples of “alkyl” as used herein include methyl, ethyl, n-propyl, n-butyl, n-pentyl, isobutyl, t-butyl, isopropyl, n-octyl, n-heptyl, ethylhexyl, Examples include, but are not limited to, cyclopentyl, cyclohexyl, cycloheptyl, adamantyl, and norbornyl. Unless otherwise noted, alkyl groups may be monovalent or polyvalent.

  As used herein, the term “heteroalkyl” is a straight, branched, and cyclic alkyl group having one or more heteroatoms independently selected from S, O, and N. Including both unsubstituted and substituted alkyl groups. Unless stated otherwise, heteroalkyl groups typically contain from 1 to 20 carbon atoms. “Heteroalkyl” is a subset of “hetero (hetero) hydrocarbyl” described below. Examples of “heteroalkyl” as used herein include methoxy, ethoxy, propoxy, 3,6-dioxaheptyl, 3- (trimethylsilyl) -propyl, 4-dimethylaminobutanyl and the like. However, it is not limited to these. Unless otherwise noted, heteroalkyl groups can be monovalent or polyvalent.

  As used herein, “aryl” is an aromatic containing 6-18 ring atoms and may have a fused ring which may be saturated, unsaturated or aromatic. Examples of aryl groups include phenyl, naphthyl, biphenyl, phenanthryl, and anthracyl. A heteroaryl is an aryl containing 1 to 3 heteroatoms such as nitrogen, oxygen, or sulfur, and may contain a condensed ring. Some examples of heteroaryl are pyridyl, furanyl, pyrrolyl, thienyl, thiazolyl, oxazolyl, imidazolyl, indolyl, benzofuranyl, and benzothiazolyl. Unless otherwise noted, aryl and heteroaryl groups may be monovalent or polyvalent.

  As used herein, “(hetero) hydrocarbyl” includes (hetero) hydrocarbylalkyl and aryl groups, and hetero (hetero) hydrocarbylheteroalkyl and heteroaryl groups, the latter being an ether or amino group, etc. Contains one or more catenary oxygen heteroatoms. The hetero (hetero) hydrocarbyl may optionally contain one or more catenary (intrachain) functional groups including ester, amide, urea, urethane, and carbonate functional groups. Unless otherwise stated, non-polymeric (hetero) hydrocarbyl groups typically contain 1 to 60 carbon atoms. Some examples of such (hetero) hydrocarbyls, as used herein, include methoxy in addition to those described for “alkyl”, “heteroalkyl”, “aryl”, and “heteroaryl” above. , Ethoxy, propoxy, 4-diphenylaminobutyl, 2- (2′-phenoxyethoxy) ethyl, 3,6-dioxaheptyl, 3,6-dioxahexyl-6-phenyl, but are not limited thereto. .

As used herein, the term “residue” refers to the (hetero) hydrocarbyl moiety of the group remaining after removal (or reaction) of the attached functional group or attached group in the described formula. Used to define For example, the “residue” of butyraldehyde C ₄ H ₉ —CHO is a monovalent alkyl C ₄ H ₉ —. Residues of hexamethylene diamine _{H 2 N-C 6 H 12} -NH 2 is divalent alkyl _-C 6 _{H 12} - is. The residue of phenylenediamine H ₂ N—C ₆ H ₄ —NH ₂ is divalent aryl-C ₆ H ₄ —. Residues of diamino polyethylene glycol _{H 2 N- (C 2 H 4} O) 1~20 -C 2 H 4 -NH 2 is a divalent (hetero) hydrocarbyl polyethylene glycol _{- (C 2 H 4 O)} 1~20 - C ₂ H ₄ - is.

2 is a DSC scan showing the elemental sulfur catalyst cure of benzoxazine and the effect of the ratio of benzoxazine to sulfur in the cure profiles of Comparative Example 1 and Examples 3-8. 2 is a DSC scan showing selenium-catalyzed curing of benzoxazine and the effect of the ratio of benzoxazine to selenium in the curing profiles of Comparative Example 1 and Examples 19-20. 4 is a DSC scan showing tetraphosphorus trisulfide catalyzed curing of benzoxazine and the effect of the ratio of benzoxazine to tetraphosphorus trisulfide in the curing profiles of Comparative Example 1 and Examples 42-46.

  The present disclosure is directed to a polymerizable composition comprising a benzoxazine compound and a catalyst selected from elemental sulfur, elemental selenium, and a sulfide or selenide of a Group V element or Group VI element.

  Any benzoxazine compound may be used in the preparation of polybenzoxazine. Benzoxazine can be prepared by combining a phenolic compound, an aliphatic aldehyde, and a primary amine compound. US Pat. No. 5,543,516 (Ishida) and US Pat. No. 7,041,772 (Aizawa et al.), Which are incorporated herein by reference, describe methods of forming benzoxazines. Other suitable reaction schemes for producing mono, di, and higher functional benzoxazines are described in N.C. N. Ghosh et al., Polybenzoxazine-new high performance thermosetting resins: synthesis and properties, Prog. Polym. Sci. 32 (2007), pp. 1344 to 1391.

  One suitable method for preparing the starting benzoxazine compound is illustrated by the following reaction scheme.

［式中、
各Ｒ^１は、Ｈ又はアルキル基であって、脂肪族アルデヒドの残基であり、
Ｒ^２は、Ｈ、共有結合、又は多価（ヘテロ）ヒドロカルビル基、好ましくは、Ｈ、共有結合、又は二価アルキル基であり、
Ｒ^５は、一級アミノ化合物Ｒ_５（ＮＨ_２）_ｍ（式中、ｍは１〜４である）の（ヘテロ）ヒドロカルビル残基であり、
ｘは、少なくとも１である。］

[Where:
Each R ¹ is H or an alkyl group and is a residue of an aliphatic aldehyde;
R ² is H, a covalent bond, or a polyvalent (hetero) hydrocarbyl group, preferably H, a covalent bond, or a divalent alkyl group;
R ⁵ is a (hetero) hydrocarbyl residue of the primary amino compound R ₅ (NH ₂ ) _m , where m is 1-4.
x is at least 1. ]

  When polymerized, the compound of formula II is opened to produce a poly (benzoxazine) polymer of general formula III and / or IV. Analytical data shows that the poly (benzoxazine) represented by Formula III is predominant.

［式中、
各Ｒ^１は、Ｈ又はアルキル基であって、脂肪族アルデヒドの残基であり、
Ｒ^２は、Ｈ、共有結合、又は多価（ヘテロ）ヒドロカルビル基、好ましくは、Ｈ、共有結合、又は二価アルキル基であり、
Ｒ^５は、一級アミノ化合物Ｒ^５（ＮＨ_２）_ｍ（式中、ｍは１〜４である）の（ヘテロ）ヒドロカルビル残基であり、
ｙ及びｚは、少なくとも２である。］

[Where:
Each R ¹ is H or an alkyl group and is a residue of an aliphatic aldehyde;
R ² is H, a covalent bond, or a polyvalent (hetero) hydrocarbyl group, preferably H, a covalent bond, or a divalent alkyl group;
R ⁵ is a (hetero) hydrocarbyl residue of the primary amino compound R ⁵ (NH ₂ ) _m , where m is 1-4.
y and z are at least 2. ]

  Monophenols are illustrated for simplicity. Mono- or polyphenol compounds may be used. Phenol compounds that can be further substituted without limitation are desirable. For example, the 3, 4, and 5 positions of the phenolic compound may be hydrogen, or alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, aralkyl, heteroaralkyl, alkoxy, alkoxyalkylene, hydroxylalkyl, hydroxyl, Other suitable substituents such as haloalkyl, carboxyl, halo, amino, aminoalkyl, alkylcarbonyloxy, alkyloxycarbonyl, alkylcarbonyl, alkylcarbonylamino, aminocarbonyl, alkylsulfonylamino, aminosulfonyl, sulfonic acid, or alkylsulfonyl May be substituted. Desirably, at least one of the ortho positions relative to the hydroxyl group is unsubstituted to facilitate benzoxazine ring formation.

  The aryl ring of the phenolic compound may be a phenyl ring as depicted or may be selected from naphthyl, biphenyl, phenanthryl, and anthracyl. The aryl ring of the phenol compound may further include a heteroaryl ring containing 1 to 3 heteroatoms such as nitrogen, oxygen, or sulfur, or may contain a condensed ring. Some examples of heteroaryl are pyridyl, furanyl, pyrrolyl, thienyl, thiazolyl, oxazolyl, imidazolyl, indolyl, benzofuranyl, and benzothiazolyl.

  Examples of monofunctional phenols include phenol, cresol, 2-bromo-4-methylphenol, 2-aliphenol, 4-aminophenol, and the like. Examples of bifunctional phenols (polyphenol compounds) include phenolphthalein, biphenol, 4-4′-methylene-di-phenol, 4-4′-dihydroxybenzophenone, bisphenol-A, 1,8-dihydroxyanthraquinone, 1 , 6-dihydroxynaphthalene, 2,2′-dihydroxyazobenzene, resorcinol, fluorene bisphenol and the like. Examples of trifunctional phenols include 1,3,5-trihydroxybenzene and the like.

Aldehyde reactants used in the preparation of the benzoxazine starting material include formaldehyde, paraformaldehyde, polyoxymethylene, and aldehydes having the general formula R ¹ CHO, where R ¹ is H or an alkyl group. Including mixtures of such aldehydes, preferably having 1 to 12 carbon atoms. The R ¹ group may be linear or branched, cyclic or acyclic, saturated or unsaturated, or combinations thereof. Other useful aldehydes include crotonaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, and heptaldehyde.

  Amino compounds useful in the preparation of the starting benzoxazines may be substituted or unsubstituted, monosubstituted, disubstituted, or more substituted (hetero) hydrocarbylamines having at least one primary amine group. The amine may be an aliphatic amine or an aromatic amine. It may be substituted with groups such as alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, aralkyl, or heteroaralkyl.

Amines useful in the preparation of the starting benzoxazine compounds include amines of the formula R ⁵ (NH ₂ ) _m , including (hetero) hydrocarbyl monoamines and polyamines. R ⁵ may be a (hetero) hydrocarbyl group having valence m and is the residue of a mono-, di-, or more amine having at least one primary amine group. R ⁵ can be alkyl, cycloalkyl, or aryl, and m is 1-4. R ⁵ is preferably monovalent and polyvalent (hetero) hydrocarbyl (ie alkyl and aryl compounds having 1 to 30 carbon atoms, or heteroalkyl and heteroaryl having 1 to 20 heteroatoms of oxygen. (Hetero) hydrocarbyl). In some embodiments, R ⁵ is a poly (alkyleneoxy) group, such as a poly (ethyleneoxy), poly (propyleneoxy), or poly (ethyleneoxy-co-propyleneoxy) group.

In one embodiment, R ⁵ comprises a non-polymeric aliphatic, alicyclic, aromatic, or alkyl-substituted aromatic moiety having 1 to 30 carbon atoms. In another embodiment, R ⁵ comprises a polymeric polyoxyalkylene, polyester, polyolefin, poly (meth) acrylate, polystyrene, or polysiloxane polymer having pendant or terminal reactive —NH ₂ groups. Useful polymers include, for example, amine-terminated oligo- and poly- (diaryl) siloxanes, and (dialkyl) siloxane amino-terminated polyethylenes or polypropylenes, and amino-terminated poly (alkylene oxides). Useful polyamines also include polydialkylsiloxanes having pendant or terminal amino groups.

  Any primary amine may be used. Useful monoamines include, for example, methyl-, ethyl-, propyl-, hexyl-, octyl, dodecyl-, dimethyl-, methylethyl-, and aniline. The term “di- or polyamine” refers to an organic compound containing at least two primary amine groups. Aliphatic, aromatic, cycloaliphatic, and oligomeric di- and polyamines are all considered useful in the practice of the present invention. A representative class of useful di- or polyamines is 4,4'-methylenedianiline, 3,9-bis- (3-aminopropyl) -2,4,8,10-tetraoxaspiro [5,5 ] Undecane and polyoxyethylenediamine. Useful diamines include N-methyl-1,3-propanediamine, N-ethyl-1,2-ethanediamine, 2- (2-aminoethylamino) ethanol, pentaethylenehexamine, ethylenediamine, and N-methylethanol. Examples include amines and 1,3-propanediamine.

Examples of useful polyamines are polyamines having at least two amino groups, wherein at least one of the amino groups is primary and the rest are primary, secondary, or combinations thereof Is mentioned. _{Examples, H 2 N (CH 2 CH} 2 NH) 1~10 H, H 2 N (CH 2 CH 2 CH 2 CH 2 NH) 1~10 H, H 2 N (CH 2 CH 2 CH 2 CH 2 _{CH 2 CH 2 NH) 1~10 H} , H 2 N (CH 2) 3 NHCH 2 CH = CHCH 2 NH (CH 2) 3 NH. ₂ , H ₂ N (CH ₂ ) ₄ NH (CH ₂ ) ₃ NH ₂ , H ₂ N (CH ₂ ) ₃ NH (CH ₂ ) ₄ NH (CH ₂ ) ₃ NH ₂ , H ₂ N (CH ₂ ) ₃ NH _{(CH 2) 2NH (CH 2} ) 3 NH 2, H2N (CH 2) 2 NH (CH 2) 3 NH (CH 2) 2 NH 2, H2N (CH 2) 3 NH (CH 2) 2 NH 2, C ₆ H ₅ NH (CH ₂ ) ₂ NH (CH ₂ ) ₂ NH ₂ , and N (CH ₂ CH ₂ NH ₂ ) ₃ , and linear or branched (including dendrimer) homopolymers, and copolymers of ethyleneimine High molecular polyamines such as (that is, aziridine). Many such compounds are described, for example, in Aldrich Chemical Company, Milwaukee, WI or Pfaltz and Bauer, Inc. , Waterbury, CN, and other common chemical suppliers.

  In some embodiments, benzoxazines derived from aliphatic polyamines including poly (alkyleneoxy) polyamines are preferred. As used herein, the phrase “derived from” refers to a structural limitation of a benzoxazine containing a polyamine residue and does not limit the process. Polybenzoxazines derived from aliphatic polyamines have been found to be more flexible (dynamic mechanical analysis, as measured by DMA) than polybenzoxazines derived from aromatic amines such as aniline. Yes. A benzoxazine derived from such an aliphatic amine can be copolymerized with a benzoxazine derived from an aromatic amine to provide a copolymerizable polybenzoxazine.

The aliphatic polyamine can also be provided by a poly (alkyleneoxy) polyamine. The resulting polybenzoxazine contains poly (alkyleneoxy) polyamine residues. Poly (alkyleneoxy) polyamines useful in the preparation of benzoxazines for subsequent polymerization can be selected from the following structures.
H ₂ N—R ⁶ —O— (R ⁷ O) _p — (R ⁸ O) _q — (R ⁷ O) _r —R ⁶ —NH ₂ , that is, poly (alkyleneoxy) diamine, or [H ₂ N ^{_{-R 6 O- (R 7 O)}} p -] s -R 9,
In the formula, R ⁶ , R ⁷ and R ⁸ are alkylene groups having 1 to 10 carbon atoms and may be the same or different. Preferably, R ⁶ is an alkyl group having 2 to 4 carbon atoms, such as ethyl, n-propyl, isopropyl, n-butyl, or isobutyl. Preferably R ⁷ and R ⁸ are alkyl groups having 2 or 3 carbon atoms, such as ethyl, n-propyl, or isopropyl. R ⁹ is the residue of the polyol used to prepare the poly (alkyleneoxy) polyamine (ie, the organic structure remaining when the hydroxyl group is removed). R ⁹ may be branched or straight chain and may be substituted or unsubstituted (but the substituent must not interfere with the oxyalkylation reaction).

  The value of p is 1 or more, more preferably greater than about 1 and 150 or less, most preferably greater than about 1 and 20 or less. Structures where p is 2, 3, or 4 are also useful. The values of q and r are both 0 or more. The value of s is greater than 2, more preferably 3 or 4 (so as to provide polyoxyalkylene triamine and tetraamine, respectively). The values of p, q, r, and s are preferably selected so that the resulting complex is a liquid at room temperature because handling and mixing are simple. Usually, the poly (alkyleneoxy) polyamine is itself a liquid. In the case of polyoxyalkylene, a molecular weight of less than about 5,000 may be used, but a molecular weight of about 1,000 or less is more preferred, and a molecular weight of about 250 to 1,000 is most preferred.

  Examples of particularly preferred poly (alkyleneoxy) polyamines include polyethylene oxide diamine, polypropylene oxide diamine, polypropylene oxide triamine, diethylene glycol propylene diamine, triethylene glycol propylene diamine, polytetramethylene oxide diamine, polyethylene oxide-co-polypropylene oxide diamine, And polyethylene oxide-co-polypropylene oxide triamine.

  Examples of suitable commercially available poly (alkyleneoxy) polyamines include D, ED, and EDR series diamines (eg, D-400, D-2000, D-5000, ED-600, ED-900, ED-2001). And EDR-148), and various JEFFAMINES from Huntsman Chemical Company, such as T series triamines (e.g., T-403), and H221 from Union Carbide Company.

  Many di- and polyamines, such as those described above, are commercially available, such as those available from Huntsman Chemical, Houston, TX. Most preferred di- or polyamines include aliphatic di- and triamines or aliphatic di- or polyamines, more specifically two or three primary amino groups such as ethylenediamine, hexamethylenediamine, dodecanediamine and the like. The compound which has is mentioned. Useful commercially available polydialkylsiloxanes having terminal or pendant amine groups include PDMS Diamond 5k, 10k, or 15k from 3M Company, or Th. Tegomer ™ A-Si 2120 or 2130 from Goldschmidt, or DMS ™ -A11, A12, A15, A25 or A32 from Gelest, AMS ™ -132, 152, 162, and 232, ATM ™ ) -1112, or Rhodosil ™ 21634 and 21644, 21642 and 21737 from Rhone-Poulenc.

  Other useful amines include amino acids such as glycine, alanine, and leucine, and polyamino acids including amino alcohols such as methyl esters, ethanolamine, 3-aminopropanol, and 4-aminobutanol, ethylene glycol, and diethylene glycol. Examples include ethers (such as Jeffamine ™ diamine) and alkenylamines such as allylamine and butenylamine.

It is understood that monoamines cyclize with aldehydes and phenolic compounds to produce mono-benzoxazine compounds, while di- or higher amines cyclize to produce di- and poly-benzoxazine compounds. The
For example, a diamine (in Scheme VI below, where m = 2) produces a dibenzoxazine.

［式中、各Ｒ^１は、Ｈ又はアルキル基であって、脂肪族アルデヒドの残基であり、
Ｒ^２は、Ｈ、共有結合、又は多価（ヘテロ）ヒドロカルビル基、好ましくは、Ｈ、共有結合、又は二価アルキル基であり、
Ｒ^５は、一級アミノ化合物の（ヘテロ）ヒドロカルビル残基である。］

Wherein each R ¹ is H or an alkyl group and is a residue of an aliphatic aldehyde;
R ² is H, a covalent bond, or a polyvalent (hetero) hydrocarbyl group, preferably H, a covalent bond, or a divalent alkyl group;
R ⁵ is a (hetero) hydrocarbyl residue of a primary amino compound. ]

  In addition, polymeric benzoxazines can be prepared from polyphenolic compounds such as bisphenol-A, and di- or polyamines, which may be further ring-opening polymerized according to the methods described herein.

［式中、
各Ｒ１は、Ｈ又はアルキル基であって、脂肪族アルデヒドの残基であり、
Ｒ^２は、Ｈ、共有結合、又は多価（ヘテロ）ヒドロカルビル基、好ましくは、Ｈ、共有結合、又は二価アルキル基であり、
Ｒ^４は、一級アミノ化合物の（ヘテロ）ヒドロカルビル残基であり、
Ｒ^５は、一級アミノ化合物の（ヘテロ）ヒドロカルビル残基であり、
ｚは、少なくとも１、好ましくは２以上である。］

[Where:
Each R1 is H or an alkyl group and is a residue of an aliphatic aldehyde;
R ² is H, a covalent bond, or a polyvalent (hetero) hydrocarbyl group, preferably H, a covalent bond, or a divalent alkyl group;
R ⁴ is a (hetero) hydrocarbyl residue of a primary amino compound;
R ⁵ is a (hetero) hydrocarbyl residue of a primary amino compound;
z is at least 1, preferably 2 or more. ]

  In some preferred embodiments, the polymerizable composition comprises a benzoxazine derived from an arylamine. In some embodiments, the polymerizable composition comprises a benzoxazine derived from an aliphatic amine. In some preferred embodiments, the polymerizable composition comprises a mixture of benzoxazines derived from both aliphatic and aryl amines. Preferably, in such embodiments, the aliphatic polyamine is a poly (alkyleneoxy) di- or polyamine.

The catalyst of the polymerizable composition is selected from elemental sulfur, elemental selenium, or sulfides or selenides of group V or group VI elements, but the melting point of the additional catalyst selected is the benzo used. The condition is that it is lower than the autocatalytic temperature of oxazine. For the example BZ-1, the autocatalytic temperature is approximately 240 ° C. Any crystalline or amorphous form of elemental sulfur can be used. Elemental sulfur, nominally, are described as S ₈ rings, are known other polymers and oligomers. Any allotropic form of the elemental selenium can be used. Nominally, selenium sulfide, refers to many different compounds of sulfur and selenium, generally are given formula SeS _2. Phosphorous trisulfide, phosphorous pentasulfide, and tetrasulfur tetranitride can be used. The catalyst is generally used in a molar amount of 0.1 to 10% relative to the amount of benzoxazine. Beyond this amount, analysis reveals significant degradation of the benzoxazine ring relative to the amount of poly (benzoxazine) formed. Preferably, the catalyst is used in an amount of 0.1-5 mole percent, most preferably 0.1-2 mole percent.

Polymerization of a benzoxazine monomer to a polymer is believed to be an ionic ring-opening polymerization that converts the oxazine ring to another structure, such as a linear polymer or a larger heterocyclic ring. The chain transfer process is believed to limit the molecular weight of the resulting polymer, resulting in some branching. B. Meyer (Chemical Reviews, 1976, vol. 76 (3)) reports that many reactive species are formed by elemental sulfur in the lysate. R. reported that elemental sulfur forms charge transfer complexes in the presence of primary or secondary amines. E. A study by Davis et al. (JASC, 84 (11) p. 2085, 1962) further suggests the action of ions. As is known, NMR spectroscopy can be used to monitor the conversion of benzoxazine monomers to polymers, or general formulas III and / or IV, resulting in phenoxy and phenol repeat units. Catalyst residues can be detected in the polymer matrix. No evidence was pointed out that sulfur was incorporated into the polymer.

［式中、
各Ｒ^１は、Ｈ又はアルキル基であって、脂肪族アルデヒドの残基であり、
Ｒ^２は、Ｈ、共有結合、又は多価（ヘテロ）ヒドロカルビル基、好ましくはＨ、共有結合、又は二価アルキル基であり、
Ｒ^５は、一級アミノ化合物Ｒ_５（ＮＨ^２）_ｍ（式中、ｍは１〜４である）の（ヘテロ）ヒドロカルビル残基であり、
ｙ及びｚは、少なくとも２である。］

[Where:
Each R ¹ is H or an alkyl group and is a residue of an aliphatic aldehyde;
R ² is H, a covalent bond, or a polyvalent (hetero) hydrocarbyl group, preferably H, a covalent bond, or a divalent alkyl group;
R ⁵ is a (hetero) hydrocarbyl residue of the primary amino compound R ₅ (NH ² ) _m , where m is 1-4.
y and z are at least 2. ]

  The reaction conditions for curing the composition depend on the reactants and amounts used and can be determined by one skilled in the art. The polymerizable composition is made by mixing the benzoxazine compound and the catalyst described above with any compound, oligomer, or polymer in any order. Generally, the composition is then heated to a temperature of about 50-200 ° C, preferably about 130-180 ° C for about 1-120 minutes. In many embodiments, the mixture is heated to a first temperature above the melting point of benzoxazine to form a homogeneous mixture, where the catalyst is dissolved in molten benzoxazine and then a second high Heat to the starting temperature, where polymerization to poly (benzoxazine) occurs. Usually, the polymerization is carried out without a solvent.

  Suitable heat sources for curing the compositions of the present invention include induction heating coils, ovens, hot plates, heat guns, infrared sources including lasers, and microwave sources. Suitable light sources and radiation sources include ultraviolet light sources, visible light sources, and electron beam sources.

  In some embodiments, the polymerizable composition may further include a film forming agent, which may include a reactive diluent, a toughening agent, and a film forming polymer. These materials, as the name suggests, allow the formation of benzoxazine-containing films. Such a film is preferably flexible and tacky over a desired temperature window ranging from sub-ambient temperature to the cure temperature of benzoxazine. The film forming agent may be non-reactive with benzoxazine or the catalyst, or both may be reactive.

  In some embodiments, the film former is an oligomer or polymer that forms a homogeneous mixture with the benzoxazine / catalyst mixture, preferably at processing temperatures from sub-ambient temperature to processing of the polymerizable benzoxazine composition. . The catalyst present in these films provides excellent shelf life even when the films are stored at high temperatures.

  If desired, the film former may have reactive functional groups that react with a portion of the benzoxazine. Examples of such reactive functional groups include, but are not limited to, amines, thiols, alcohols, epoxides, and vinyls. In some embodiments, the toughening agent or reactive diluent may include reactive end groups. The presence of such functional groups can increase the processability options of the film, and the film can be processed above or below the reaction temperature of the reactive group to achieve different degrees of tackiness, acceptable. Flexibility and other desirable properties can be provided. Examples of such reactive film formers include amine-terminated butadiene nitriles (ATBN), hydroxy-terminated butadiene nitriles (HOTBN), carboxy-terminated butadiene nitriles CTBN, amine-terminated poly (alkylene oxides) (Jeffamine ™ and Versalink ( And the like, and related compounds.

  In some embodiments, the reactive film former may have different reactive groups on its backbone and ends. Examples of such materials include end functional butadiene nitrile rubbers such as ATBN, which have unsaturation at the repeat unit and an amine functional reactive group at the end. Amine functional groups can react with benzoxazine by nucleophilic ring opening, and unsaturation can react with the catalyst by vulcanization.

  As explained, the polymerizable composition may further comprise a toughening agent. Reinforcing agents useful in the present invention are polymeric compounds having both a rubber phase and a thermoplastic phase, such as polymerized, diene, rubbery cores and graft polymers having a polyacrylate polymethacrylate shell; rubbery polyacrylate cores. And graft polymers having a polyacrylate or polymethacrylate shell; and elastomer particles that are polymerized in situ in epoxides from free radical polymerizable monomers and copolymerizable polymer stabilizers.

Examples of the first type of useful toughener include acrylate or methacrylic acid, as disclosed in US Pat. No. 3,496,250 (Czerwinski), incorporated herein by reference. And graft copolymers having a polymerized diene rubbery backbone or core onto which the shell of the ester is grafted, monovinyl aromatic hydrocarbons, or mixtures thereof. Preferred rubbery backbones include polymerized butadiene or a mixture of butadiene and styrene polymerized. A preferred shell containing polymerized methacrylic acid esters is methacrylate substituted with lower alkyl (C ₁ -C ₄ ). Preferred monovinyl aromatic hydrocarbons are styrene, alpha methyl styrene, vinyl toluene, vinyl xylene, ethyl vinyl benzene, isopropyl styrene, chlorostyrene, dichlorostyrene, and ethyl chlorostyrene. It is important that the graft copolymer does not contain functional groups that are detrimental to the catalyst.

  An example of a second type of useful toughener is an acrylate core-shell graft copolymer, where the core or backbone has a glass transition temperature of less than about 0 ° C., for example about 25 such as polymethyl methacrylate. Polybutyl acrylate or polyisooctyl acrylate grafted with a polymethacrylate polymer (shell) having a glass transition temperature above 0C.

A third class of toughening agents useful in the present invention includes elastomer particles having a glass transition temperature (T _g ) of less than about 25 ° C. prior to mixing with the other components of the composition. These elastomer particles are polymerized from a free-radically polymerizable monomer and a copolymerizable polymer stabilizer that is soluble in benzoxazine. Free radical polymerizable monomers are diisocyanates combined with ethylenically unsaturated monomers or co-reactive bifunctional hydrogen compounds such as diols, diamines, and alkanolamines.

  Useful reinforcing agents include core / shell polymers such as methacrylate-butadiene-styrene (MBS) copolymers where the core is a cross-linked styrene / butadiene rubber and the shell is polymethyl acrylate (eg, Rohm and Haas, Philadelphia, PA ACRYLOID KM 653 and KM 680 available from), cores containing polybutadiene and shells containing poly (methyl methacrylate) (eg, Kane ACE M511, M521, B11A, B22 available from Kaneka Corporation, Houston, TX) B31 and M901, and CLEARSTRENGTH C223 available from ATOFINA, Philadelphia, PA), polyshiro Having a sun core and polyacrylate shell (eg CLEARSTRENGTH S-2001 available from ATOFINA and Wacker-Chemie GmbH, GENIOPERL P22 available from Wacker Silicones, Munich, Germany), polyacrylate core and poly (methyl methacrylate) shell (E.g., PARALOID EXL2330 available from Rohm and Haas, and STAPHYLOID AC3355 and AC3395 available from Takeda Chemical Company, Osaka, Japan), MBS core and poly (methyl methacrylate) shell (e.g., Rohm) and from Haas Possible PARALOID EXL2691A, EXL2691 and EXL2655), etc., and mixtures thereof. Preferred modifiers include the ACRYLOID and PARALOID modifiers listed above, and mixtures thereof.

As used above, a “core” with respect to an acrylic core / shell material is understood to be an acrylic polymer having a T _{g of} <0 ° C., and a “shell” is an acrylic having a T _{g of} > 25 ° C. It is understood to be a polymer.

  Other useful toughening agents include carboxylated and amine-terminated acrylonitrile / butadiene vulcanizable elastomer precursors such as Hycar ™ CTBN 1300X8 and ATBN 1300X16 and Hycar ™ 1072 (BF Goodrich Chemical Co.). Butadiene polymers such as Hycar ™ CTB, amine functional polyethers such as HCl 101 (ie polytetramethylene oxide diamine), 10,000 MW primary amine-terminated compounds (Minnesota Mining and Manufacturing Co. (St. Paul, Minn.)), And Jeffamine (TM) (Huntsman Chemical Co. (Houston, Tex.)), Functional acrylic rubbers containing an acrylic core / shell material, such as Acryloid ™ KM330 and 334 (Rohm & Haas), and core / shell polymers, such as methacrylate butadiene styrene (MBS) copolymers, in which the core is crosslinked / Butadiene rubbers with shells of polymethyl acrylate (eg, Acryloid ™ KM653 and KM680 (Rohm and Haas). Useful liquid polybutadiene hydroxyl terminated resins include the trade name “Liquiflex H” ( Petroflex (Wilmington, Delaware)) and "HT 45" (Sartomer (Exton, Pennsylvania)).

  The toughening agent may include an epoxy terminated compound, which can be incorporated into the polymer backbone. A list of typical preferred toughening agents includes acrylic core / shell polymers, styrene butadiene / methacrylate core / shell polymers, polyether polymers, carboxylated acrylonitrile / butadiene, and carboxylated butadiene. Even in the absence of the reinforcing agent described above, benefits can be obtained from the conditions of the chain extender in the composition having an epoxy resin. However, certain benefits can be obtained from the presence of a toughener or a combination of different agents, as already proposed. As disclosed herein, it is a feature of the present invention that improved resins are generally made particularly susceptible to, or enhanced with respect to, the efficacy of the toughener.

  The toughening agent is useful in an amount equal to about 3-35%, preferably about 5-25% by weight of the benzoxazine. The toughening agent of the present invention imparts strength to the cured composition without reacting with benzoxazine or interfering with curing.

  It will be appreciated that some of the natural and synthetic rubbers described have unsaturated bonds in the chain that can be crosslinked to the catalyst. Thus, the catalyst polymerizes benzoxazine and at the same time vulcanizes the rubber into an extensive network of poly (benzoxazine) and vulcanized rubber.

In some embodiments, the polymerizable composition may further comprise a reactive diluent having at least one nucleophilic functional group that opens the benzoxazine. Nucleophilic compounds have the general formula:
R ⁸ − (ZH) _p , XV
It is represented by
Where
R ⁸ is a (hetero) hydrocarbyl group;
Z is or —S—, or —NR ⁹ , wherein R ⁹ is H or a hydrocarbyl group such as aryl and alkyl;
p is 1-6, preferably at least 2.

  The ring opening reaction can be represented by the following schemes XX and XXI.

［式中、
各Ｒ^１は、Ｈ又はアルキル基であって、脂肪族アルデヒドの残基であり、
Ｒ^２は、Ｈ、共有結合、又は多価（ヘテロ）ヒドロカルビル基、好ましくはＨ、共有結合、又は二価アルキル基であり、
Ｒ^５は、一級アミノ化合物の（ヘテロ）ヒドロカルビル残基であり、
Ｒ^８は、（ヘテロ）ヒドロカルビル基であり、
Ｚは、−Ｓ−又は−ＮＲ^９（式中、各Ｒ^９は、Ｈ、又はアリール及びアルキルを含むヒドロカルビル基である。）の混合物であり、
ｐは、１〜６であり、
ｑは、繰り返し単位の数であって、少なくとも１、好ましくは少なくとも２である。］

[Where:
Each R ¹ is H or an alkyl group and is a residue of an aliphatic aldehyde;
R ² is H, a covalent bond, or a polyvalent (hetero) hydrocarbyl group, preferably H, a covalent bond, or a divalent alkyl group;
R ⁵ is a (hetero) hydrocarbyl residue of a primary amino compound;
R ⁸ is a (hetero) hydrocarbyl group;
Z is, -S- or -NR ⁹ (wherein each ^{R 9} is, H, or a hydrocarbyl group containing aryl and alkyl.) A mixture of,
p is 1-6,
q is the number of repeating units and is at least 1, preferably at least 2. ]

Note that in Schemes XX and XXI, and other schemes herein, the product represents a mixture of free thiol and / or amine groups “Z”. This notation is used to describe all Z groups present in the starting material that can be used for subsequent reactions. Thus, the starting bis-benzoxazine reacts with a mixture of amine compound and / or thiol R ⁴ (SH) _n and the initial reaction product can be used for further reaction with additional benzoxazine groups. It has a possible "n-1" Z group. Furthermore, in embodiments where the starting benzoxazine is prepared with a polyamine, the R ⁵ group can be linked to an additional benzoxazine group. It is further noted that the polymer reaction product results when the composition includes at least one multifunctional thiol compound or amine compound.

In these embodiments, the unreacted benzoxazine is homopolymerized in the presence of a catalyst to have the same broadening of the reactive diluent represented by Formula XV and the poly (benzoxazine) and benzoxazine adduct. There is an excess of benzoxazine so as to form a mixture or polymer network. In such embodiments, the total and molar ratio of amine and / or thiol “Z” groups derived from the benzoxazine group and the compound R ⁸ — (ZH) _p is about 3: 1 to 100: 1, preferably 4: 1 to 50: 1.

Reactive diluent R ⁸ - With regard to (ZH) _p, benzoxazine ring can be opened with an amine compound. Useful amine compounds correspond to primary and secondary amines represented by the formula below and include primary and secondary (hetero) hydrocarbyl monoamines and polyamines.
R ¹⁰ (NHR ⁹ ) _m , XII
R ¹⁰ can be a (hetero) hydrocarbyl group having valence m and is the residue of a mono-, di-, or higher amine having at least one primary amine group. R ¹⁰ can be alkyl, cycloalkyl, or aryl, and m is 1-4. R ¹⁰ is preferably selected from monovalent and polyvalent (hetero) hydrocarbyl (ie, alkyl and aryl compounds having 1 to 30 carbon atoms, or heterocycles having 1 to 20 oxygen heteroatoms. (Hetero) hydrocarbyl such as alkyl and heteroaryl). Each R ⁹ is independently H or a hydrocarbyl group containing aryl and alkyl, and m is 1-6. It will be apparent to those skilled in the art that the same amine used in the preparation of benzoxazine (above) is also useful in ring opening reactions.

The benzoxazine ring has the formula:
_{^{R 4 - (SH) n,}} VII
Rings can also be opened with the thiol represented by (wherein n is 1 to 6). R ⁴ includes any (hetero) hydrocarbyl group, such as aliphatic and aromatic monothiols and polythiols. R ⁴ may optionally further comprise one or more functional groups such as hydroxyl, acid, ester, cyano, urea, urethane and ether groups.

In some preferred embodiments, the thiol compound has the formula:
_{^{R 6 - [(CO 2)}} x -R 7 -SH] y, VIII
(Where
R ⁶ is an alkylene group, an aryl group, an oxyalkylene group, or a combination thereof, R ⁷ is a divalent hydrocarbyl group, x is 0 or 1, and y is 1-6. ).

  Useful thiol compounds that fall within the scope of Formula VII include the following formulas:

（式中、
Ｒ^６は、アルキレン基、アリール基、オキシアルキレン基、又はそれらの組み合わせであり、
Ｒ^７は、二価ヒドロカルビル基であり、
ｘは、０又は１であり、
ｙは、１〜６である。）
で表されるチオールが挙げられる。
好ましくは、式ＩＸ〜ＸＩの化合物は、Ｒ^６がアルキレン基であるものである。

(Where
R ⁶ is an alkylene group, an aryl group, an oxyalkylene group, or a combination thereof;
R ⁷ is a divalent hydrocarbyl group;
x is 0 or 1,
y is 1-6. )
The thiol represented by these is mentioned.
Preferably, compounds of formulas IX-XI are those wherein R ⁶ is an alkylene group.

  Useful alkyl thiols include methyl, ethyl and butyl thiol, as well as 2-mercaptoethanol, 3-mercapto-1,2-propanediol, 4-mercaptobutanol, mercaptoundecanol, 2-mercaptoethylamine, 2,3- Dimercaptopropanol, 3-mercaptopropyltrimethoxysilane, mercaptoalkanoic acid and its esters including mercaptopropionic acid, 2-chloroethanethiol, 2-amino-3-mercaptopropionic acid, dodecyl mercaptan, thiophenol, 2-mercaptoethyl ether And pentaerythritol tetrathioglycolate. Specific examples of useful polythiols include dimercaptodiethyl sulfide; 1,6-hexanedithiol; 1,8-dimercapto-3,6-dithiaoctane; propane-1,2,3-trithiol; And [(2-mercaptoethyl) thio] -3-mercaptopropane; tetrakis (7-mercapto-2,5-dithiaheptyl) methane; and trithiocyanuric acid.

  Another useful class of polythiols includes polyols and thiol-terminated carboxylic acids (or esters or acyl halides) including α- or β-mercaptocarboxylic acids such as thioglycolic acid or β-mercaptopropionic acid or esters thereof. And their derivatives) and those obtained by esterification. Useful examples of the compound thus obtained include ethylene glycol bis (thioglycolate), pentaerythritol tetrakis (3-mercaptopropionate), ethylene glycol bis (3-mercaptopropionate), trimethylolpropane tris. (Thioglycolate), trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (thioglycolate) pentaerythritol tetrakis (3-mercaptopropionate), and these are all commercially available. A specific example of a preferred polymeric polythiol is polypropylene ether glycol bis (3-mercaptopropionate), which can be converted to polypropylene-ether glycol (eg, Pluracol ™ P201, BASF Wyandotte Chemical Corp) by esterification. .) And 3-mercaptopropionic acid.

In some embodiments, useful thiols include thiols derived from epoxy compounds. The polythiol can be derived from a reaction between H ₂ S (or equivalent) and an epoxy resin having two or more functional groups and preferably having a molecular weight of less than 1000. For example, bifunctional epoxy resins such as bisphenol A epoxy resin and bisphenol F epoxy resin, and novolac epoxy resins such as phenol novolac epoxy resin and cresol novolac epoxy resin, or amine epoxy resins can be used. Furthermore, generally known polyfunctional epoxy resins, heterocyclic ring-containing epoxy resins, and alicyclic epoxy resins can be used. These epoxy resins may be used alone or in combination of two or more chemical types or molecular weight ranges.

  Particularly useful polythiols are those derived from bisphenol A diglycidyl ether available from Japan Epoxy Resins as QX-11 having a thiol equivalent of about 245 and the following general structure (n is at least 1): .

  Useful soluble high molecular weight thiols include polyethylene glycol di (2-mercaptoacetate), LP-3 ™ resin supplied by LP North America (Houston, TX), and Products Research & Chemical Corp. Examples include compounds such as Permapol P3 ™ resin supplied by (Glendale, Calif.) And adducts of 2-mercaptoethylamine and caprolactam.

  Compounds represented by Schemes XX and XXI can be prepared by combining a benzoxazine compound and a reactive diluent represented by Formula XV as is or in a suitable solvent. Suitable solvents include those in which the reaction reagent is preferably dissolved at room temperature. Solvents can include those that are non-reactive with the reaction reagent and those that subsequently dissolve the co-reaction reagent. Examples of suitable solvents include butyl acetate, toluene, xylene, tetrahydrofuran, ethylene glycol dimethyl ether and the like. Since the ring opening induced by thiols and amines is exothermic, heating is usually unnecessary.

  The reactive diluent can include an epoxy resin. Epoxy groups do not react directly with benzoxazine like amines or thiols, but phenol groups obtained by ring opening of benzoxazine can further react to open the epoxy group.

  Polyepoxy compounds that can be utilized in the compositions of the present invention include both aliphatic and aromatic polyepoxides, with glycidyl aliphatic epoxides being preferred. An aromatic polyepoxide is a compound containing at least one aromatic ring structure, such as a benzene ring and more than one epoxy group. Preferred aromatic polyepoxides include polyglycidyl ethers of polyhydric phenols (for example, bisphenol A derivative resins, epoxy cresol-novolak resins, bisphenol F derivative resins, epoxyphenol-novolak resins) and glycidyl esters of aromatic carboxylic acids. The most preferred aromatic polyepoxide is a polyglycidyl ether of a polyhydric phenol.

  Representative examples of aliphatic polyepoxides that can be utilized in the compositions of the present invention include 3 ', 4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxycyclohexyloxirane, 2- (3', 4′-epoxycyclohexyl) -5, IH-spiro-3H 4H-epoxycyclohexane-1,3-dioxane, bis (3,4-epoxycyclohexylmethyl) adipate, diglycidyl ester of linoleic dimer acid, 1,4 Aliphatic such as bis (2,3-epoxypropoxy) butane, 4- (1,2-epoxyethyl) -1,2-epoxycyclohexane, 2,2-bis (3,4-epoxycyclohexyl) propane, glycerol Polyglycidyl ether of polyol or hydrogenated 4,4'-dihydride Carboxy diphenyl - dimethyl methane, and mixtures thereof.

  Representative examples of aromatic polyepoxides that can be used in the compositions of the present invention include glycidyl esters of aromatic carboxylic acids (eg, diglycidyl phthalate, diglycidyl isophthalate, triglycidyl trimellitic acid, and pyromellitic acid). Tetraglycidyl esters, as well as mixtures thereof), N-glycidylaminobenzene (eg, N, N-diglycidylbenzeneamine, bis (N, N-diglycidyl-4-aminophenyl) methane, 1,3-bis (N, N-diglycidylamino) benzene, and N, N-diglycidyl-4-glycidyloxybenzenamine, and mixtures thereof), and polyglycidyl derivatives of polyhydric phenols (eg, 2,2-bis- (4- (2 , 3-Epoxypropoxy) phenylpropane Polyglycidyl ethers of polyphenols (for example, tetrakis (4-hydroxyphenyl) ethane, pyrocatechol, resorcinol, hydroquinone, 4,4'-dihydroxydiphenylmethane, 4,4'-dihydroxydiphenyldimethylmethane, 4,4'- Dihydroxy-3,3′-dimethyldiphenylmethane, 4,4′-dihydroxydiphenylmethylmethane, 4,4′-dihydroxydiphenylcyclohexane, 4,4′-dihydroxy-3,31-dimethyldiphenylpropane, 4,4′-dihydroxy Diphenylsulfone and tris- (4-hydroxyphenyl) methane), novolak polyglycidyl ether (reaction product of mono- or polyhydric phenols with aldehydes in the presence of an acid catalyst), and US Pat. No. 3,0 Derivatives described in US Pat. Nos. 8,262 and 3,298,998, and derivatives described in Handbook of Epoxy Resins, McGraw-Hill Book Co., New York (1967) by Lee and Neville, and mixtures thereof. Can be mentioned.

  A preferred class of polyepoxy compounds are polyglycidyl ethers of polyhydric alcohols, especially polyphenols. Glycidyl epoxy compounds are generally more reactive towards amines than cycloaliphatic epoxy compounds. In some preferred embodiments, the epoxy compound generally has an epoxy equivalent weight (EW) of 170 to about 4,000, preferably 170 to 1,000. Epoxide equivalent weight (EW) is defined as the gram weight of an epoxy functional compound containing 1 gram equivalent of epoxy (oxirane) functionality.

  The polymerizable composition may further comprise a film forming polymer. When a coating formulation containing a mixture of film-forming polymer, benzoxazine, sulfur catalyst, and optional solvent is applied to the substrate, the solvent evaporates and the polymer particles coalesce to form a continuous film with benzoxazine. However, the catalyst and other additives are dissolved or dispersed in the film-forming polymer matrix. The coating formulation is usually applied, dried and optionally heated to leave a solid coating on the finished product. Depending on the formulation, the addition of surfactants may improve the ability of the coating to wet the substrate and / or allow uniform evaporation (ie, leveling) of the solvent during film formation, thereby allowing for some films. Forming properties can be improved. The film-forming polymer can be used in an amount of 1 to 75%, preferably 10 to 50% by weight of the benzoxazine.

  Examples of suitable film-forming polymers for coating formulations include acrylic polymers (eg, poly (methyl methacrylate-co-ethyl acrylate) and poly (methyl acrylate-co-acrylic acid)); polyurethanes (eg, aliphatic, Reaction products of cycloaliphatic or aromatic diisocyanates with polyester glycols or polyether glycols); polyolefins (eg polystyrene); copolymers of styrene and acrylates (eg poly (styrene-co-butyl acrylate); polyesters ( For example, polyethylene terephthalate, polyethylene terephthalate isophthalate, and polycaprolactone); polyamides (eg, polyhexamethylene adipamide); vinyl polymers (eg, poly (vinyl acrylate)) Tate / methyl acrylate) and poly (vinylidene chloride / vinyl acetate); polydienes (eg, poly (butadiene / styrene)); cellulose derivatives including cellulose ethers and cellulose esters (eg, ethyl cellulose and cellulose acetate / butyrate), polyimides, polysulfones Such polymers are available from, for example, commercial sources, or may be prepared using methods and starting materials known in the art.

  The compositions of the present invention include coatings, foams, molded articles, adhesives (including structural and semi-structural adhesives), magnetic media, filled or reinforced composites, coated abrasives, caulking and sealing compounds, Useful for casting and molding compounds, porcelain and encapsulating compounds, impregnation and coating compounds, conductive adhesives for electronics, protective coatings for electronics, and other applications known to those skilled in the art. When uncured or partially cured, the benzoxazine composition exhibits pressure sensitive adhesive properties including tackiness. In some embodiments, the present disclosure provides a coated article comprising a substrate having a cured coating of benzoxazine thereon.

  In order to prepare structural / semi-structural benzoxazine adhesives, the polymerizable composition may contain further adjuvants such as silica fillers, glass spheres, and reinforcing agents. These adjuvants impart toughness to the polymerized composition and reduce the density.

  In some embodiments, the present disclosure provides “B-stagable” adhesives. Processing applications such as printed circuit manufacturing are to be partially polymerized into "stepped" adhesives, ie sticky or non-tacky coatings, fixed to the substrate and cured using heat, pressure, or both Often, an adhesive composition that can be used is used (see US Pat. No. 4,118,377). The tack-free stage is sometimes referred to as the “B-stage”.

  The present disclosure provides a graded adhesive composition comprising a benzoxazine compound, a film former having a reactive functional group, and a catalyst. The stageable adhesive composition can be coated onto an adherend or substrate and fully cured to a structural or semi-structural adhesive using heat.

  In one embodiment, the B-staged adhesive comprises benzoxazine, a reactive diluent of formula XV, and a catalyst. At the first temperature, the reactive diluent opens a portion of the benzoxazine to form an adduct. At the second higher temperature, the catalyst results in curing of the poly (benzoxazine).

  In another embodiment, the B-staged adhesive comprises benzoxazine, a toughening agent having a reactive functional group (such as ATBN), and a catalyst. At the first temperature, the toughener opens a portion of the benzoxazine to form an adduct. At the second higher temperature, the curing of the poly (benzoxazine) occurs by the catalyst. In some embodiments where the reinforcing agent further comprises chain unsaturation, the catalyst may vulcanize the reinforcing agent.

  In some embodiments, the partially cured staged adhesive composition is placed between two substrates (or substrates) and then heated to fully cure the adhesive, Structural and semi-structural bonding can be achieved between the substrates. In other embodiments, the graded adhesive composition may be heated to a flowable viscosity to coat the substrate, which is then bonded to the second substrate in the molten state. It may be fully cured.

  B-staged films are usually prepared by heating benzoxazine to its melting point and dissolving the desired amount of catalyst therein. Occasionally, it may be necessary to further heat the composition to near the melting point of the catalyst to ensure the desired solubility. The film former heated to the desired compounding temperature is then added to the benzoxazine / catalyst mixture and stirred until uniform, then the resulting composition between the release liners is pulled through a knife coater to obtain the desired To produce a film of thickness.

  Therefore, the present disclosure provides graded structural and semi-structural adhesives. A “half-structure adhesive” is a cured adhesive having an overlap shear strength of at least about 0.5 MPa, more preferably at least about 1.0 MPa, and most preferably at least about 1.5 MPa. However, the cured adhesive having a particularly high overlap shear strength is called a structural adhesive. A “structural adhesive” is a cured adhesive having an overlap shear strength of at least about 3.5 MPa, more preferably at least about 5 MPa, and most preferably at least about 7 MPa.

  To prepare the protective coating, the choice of material depends on the requirements of the particular application. Abrasion resistant coatings are generally hard and require a significant portion of the formulation to be a hard resin, which is typically short chain length and highly functional. Coatings that undergo some bending require toughness that can be obtained by reducing the crosslink density of the cured formulation. Clear coating requires that the cured resin has little or no phase separation. This can be obtained by controlling the compatibility of the resin or by controlling the phase separation by the cure rate. An amount of adjuvant effective for the intended use may be added to these coating formulations.

  Colorant, abrasive granule, antioxidant stabilizer, thermal decomposition stabilizer, light stabilizer, conductive particles, tackifier, fluidizer, thickener, matting agent, inert filler, binder, foaming agent Adjuvants such as fungicides, fungicides, surfactants, plasticizers, rubber tougheners, and other additives known to those skilled in the art may be added to the composition as desired. These may be substantially non-reactive materials such as inorganic fillers and organic fillers. These adjuvants, when present, are added in amounts effective for their intended purpose.

  The composition may be coated onto the substrate at a useful thickness of 25 to 500 micrometers or greater. The coating can be done by any conventional means such as a roller, dip, knife, or extrusion coating. Coating may be facilitated using a solution of the polymerizable composition. A stable thickness is necessary to form the crosslinked composition while maintaining the desired coating thickness prior to crosslinking of the composition.

  Useful substrates can be of any nature and composition and can be inorganic or organic. Representative examples of useful substrates include ceramic, glass, metal, siliceous substrates including natural and artificial stone, woven and non-woven articles, polymeric materials including thermoplastic and thermosetting (eg, polymethyl (Meth) acrylate), polycarbonate, polystyrene, styrene copolymers such as polystyrene, styrene acrylonitrile copolymer, polyester, polyethylene terephthalate), silicone, paint (such as acrylic resin based), powder coating (such as polyurethane or hybrid powder coating), and wood, Moreover, the composite material of the above-mentioned material is mentioned.

  The present disclosure further provides a pressure sensitive adhesive comprising a coating of an uncured or partially cured benzoxazine composition on a suitable substrate, such as an adhesive tape backing. A preferred method for preparing a pressure sensitive adhesive article is to partially cure the new composition to a useful coating viscosity and apply the partially crosslinked composition onto a substrate (eg, a tape backing). Coating and further curing the composition. Useful coating viscosities are generally in the range of 500 to 10,000 cps.

  All parts, percentages, ratios, etc. in the examples are by weight unless otherwise specified.

  The amount of catalyst for the adhesive is determined by the equivalent weight (eq) based on moles of reactive groups per mole of reactant molecule, for example, 2 eq of bifunctional reactant represents 1 mole of the reactant, One mole of trifunctional reactant represents 3 eq of the reactant. The catalyst is treated as being monofunctional.

  The dotted line in the table indicates that the sample was not tested.

  Unless otherwise stated, materials were obtained from Sigma-Aldrich (Milwaukee, Wis.).

Test method Differential scanning calorimetry of curing (DSC analysis)
The thermal properties of the composition during curing are determined by placing an amount of the composition in an open aluminum pan of a differential scanning calorimeter (DSC) at a heating rate of 10 ° C / min from 25 ° C to 300 ° C or 320 ° C. Measured by heating to ° C. The DSC from TA Instruments (New Castle, DE) is designated (TA) and Seiko Instruments USA, Inc. The DSC from (Torrance, CA) is designated (Seiko). Expressed in peak cure temperature (peak) expressed in degrees C from DSC trace, approximate cure temperature expressed in degrees C (onset), and joules per gram (J / g) released during curing of the composition. Report total energy (energy).

Nuclear magnetic resonance (NMR analysis)
Nuclear magnetic resonance spectra ( ¹³ C NMR, ¹ H NMR, and ⁷⁷ Se NMR) were obtained using an NMR spectrometer (Varian Inova 600 MHz NMR spectrometer with an inverted probe head with an NMR sample maintained at 25 ° C.). Measured. NMR provided information indicating the cure of the polymer and whether the catalyst was incorporated into the polymer chain.

Dynamic mechanical analysis (DMA)
Test coupons for dynamic mechanical testing were prepared by using a mold placed between two silicone release coated PET films. The mold was approximately 1.5 mm thick and formed of silicon rubber with a rectangular cutout (approximately 5 mm wide × 30 mm long) therein. An assembly was formed at the top of the mold filled with a second PET film in which the test composition was cast into a mold cutout on top of the PET film. The assembly was clamped between two glass plates and cured at 100 ° C. for 60 minutes, followed by curing at 180 ° C. for 60 minutes. The clamped assembly was then allowed to cool to room temperature. The coupons were removed and tested in a tensile mode dynamic mechanical analyzer (DMA; Seiko DMS-200, Seiko) heated to a temperature in the range of −80 ° C. to 320 ° C. at 2 ° C./min. The DMA trace from the DMA scan provides an understanding of the morphological and viscoelastic properties of the polymer when stress is applied during thermal cycling, such as the loss factor. The data also provides information on the thermal stability of the polymer.

Shrinkage Measurement The shrinkage of the cured composition was measured using a half-pipe steel mold, 25.4 cm long and 2.54 cm in diameter, coated with a silicone release coating. The mold was preheated to 100 ° C. and filled with the curable composition. The mold was then placed in an oven set at 180 ° C. for 2 hours. The mold was removed from the oven and allowed to cool to room temperature. The cured polymer bar was removed and the caliper was measured to determine the amount of shrinkage of the cured bar.

Thermogravimetric analysis (TGA)
The thermal stability of the amine-cured epoxy benzoxazine composition was measured by observation of isothermal weight loss using a thermogravimetric analysis (TGA) technique. Samples of 5-10 mg composition were placed in a thermogravimetric analyzer (TA 2950 Thermographic Analyzer) and annealed isothermally at 300 ° C, 325 ° C, 350 ° C, 375 ° C and 400 ° C. The sample was annealed for a time sufficient to result in 2.5%, 5% and 10% mass loss.

  Clint D.C. Gamlin, Naba K. et al. See Duta, Namita Roy Coudbury, Polymer Degradation and Stability 80 (2003) pp 525-531.

Data from the TGA scan was analyzed according to the Arrhenius equation where the logarithm of the thermal analysis reaction rate is proportional to the inverse of temperature. The mass loss while maintaining isothermal temperature is assumed to be due to a single reaction (or multiple single reactions), and the logarithmic plot of mass loss rate (log [change in weight / change in temperature]) vs. The reciprocal of the temperature (1 / T [° K]) produced a straight line and the gradient was obtained by R ^* Ea, where R is the general gas constant and Ea is the thermal decomposition activation energy. The higher the gradient, the greater the activation energy required for polymer degradation and the more stable the polymer.

Preparation of Test Substrate for Adhesive Bonding Properties The substrate for testing adhesive properties (Overlap Shear Strength (OLS) and Floating Roller Peel (FRP)) was a 2024 T3 bare aluminum test panel. For the OLS test, an aluminum panel of 4 in × 7 in × 0.063 in (10 cm × 18 cm × 0.16 cm) was used. For FRP test, either 8 in x 3 in x 0.063 in (20.3 cm x 7.6 cm x 0.16 cm) or 10 in x 3 in x 0.025 in (25.4 cm x 7.6 x 0.064 cm) Panel was used. The panel was treated with FPL etching, anodized with phosphoric acid and prepared as described below.

The panel was FPL etched according to the following process.
The panel was immersed in a caustic cleaning solution (Isoprep 44 solution (MacDermid Inc., Denver, CO)) at a temperature of 71 ± 10 ° C. for 10 to 11 minutes.
・ The panel was placed in a rack and submerged in a tank containing tap water for 10 minutes.
The panel was rinsed with tap water for 2-3 minutes.
A panel rake was placed in a tank of 71 ± 10 ° C. FPL etch solution (FPL solution of sulfuric acid and sodium dichromate from Forest Products Laboratory, Madison, Wis.) For 10-15 minutes.
• The etched panel was rinsed with tap water for 2-3 minutes.

  The panel rack was then anodized by submerging it in a phosphoric acid anodizing tank. The panels were anodized at a tank temperature of 67-82 ° F. (19-28 ° C.) for 23 minutes at a voltage of 15 ± 1 volts. The panel was drip dried at ambient temperature for 10 minutes and then in a 71 ° C. recirculating air oven for 30 minutes.

  Spray gun (Accumray Model 12S spray gun with 1-quart cup) so that the etched primer anodized aluminum panel has a dry primer thickness of 2.6-5.2 micrometers within 24 hours. ) Was primed with an aluminum corrosion-inhibiting adhesion primer (3M Scotch-Weld ™ Structural Adhesive Primer EW-5000 (3M Company, St. Paul, MN)) according to the manufacturer's instructions. The primed panel was dried at 75 ± 5 ° F. (24 ± 2 ° C.) for 30 minutes and then at 250 ± 5 ° F. (121 ± 2 ° C.) for 60-65 minutes.

Preparation of an uncured adhesive film incorporating a nonwoven scrim An uncured adhesive sheet between two release liners was incorporated into a nonwoven scrim as follows. One of the liners was removed and the adhesive was applied to a polyester nonwoven scrim sheet slightly larger than the adhesive film. The polyester non-woven scrim was a polyester non-woven sheet (Technical Fiber Products, Inc. (Schenectady, NY)) having a basis weight of 0.8 grams / square meter. The liner is repositioned on top of the scrim on the adhesive and the sandwich is heated with two rollers set to a temperature of 140 ° F. (60 ° C.) with a gauge pressure of 20 psi (137.9 kPa). Lamination was done using pressure from an air source. During lamination, the polyester scrim was incorporated into the adhesive between the two release liners.

Overlap Shear Strength (OLS) Test The adhesive for the OLS test is about 6 inches (15 cm) from each other so that approximately 1 inch (2.5 centimeters) of the panel extends to the opposite end without adhesive. It was placed between two aluminum panels prepared to overlap 4 in x 7 in x 0.063 in (10 cm x 18 cm x 0.16 cm). The composite was pressed together against the adhesive coated part and cured in an oven at 180 ° C. or autoclaved as defined below. The cured test panel was cut into 2.54 cm wide strips and placed on the gripping jaws of a tensile tester (MTS Systems Corporation (Eden Prairie, Minn.)). The spacing between the gripping jaws of the tester was approximately 5.5 inches (13.97 cm) and each gripping jaw gripped approximately 2.54 cm of each strip. The grasping jaws were released at a rate of 0.05 inches / minute (1.27 millimeters / minute) until failure occurred using a 30,000 pound force (13.3 kilonewtons) load cell. The gripping jaws are placed in the oven after the sample has been equilibrated to 75 ° F. (24 ° C.), 275 ° F. (136 ° C.), or 350 ° F. (177 ° C.). The test results are an average of six test samples and are reported in pounds per square inch (psi).

Floating Roller Peel (FRP) Test An uncured adhesive film supported on a scrim was prepared according to ASTM D-3167-76 with the following modifications, two prepared aluminum test panels (one with a thickness of 0. 16 cm, the other being 0.064 cm thick). A 0.5 inch (12.7 cm) wide test strip was cut along the length of the bonded aluminum panels. Each test strip was tested in a tensile tester. The thinner substrate was pulled from the thicker substrate with a peel rate of 6 inches / minute (30.5 cm / minute) and the results were normalized to a width of 1 inch (2.5 centimeters). The test results are an average of 6 test samples and are reported in 1 inch wide pounds (piw).

Autoclave curing for OLS or FRP testing A test sample was placed on a curing tray and covered with a vacuum bag. The covered tray is placed in the autoclave and an incomplete vacuum of about 28 inches Hg (95 kPa) is applied at approximately 72 ° F. (22 ° C.) for 10-15 minutes, after which the autoclave external pressure is 45 psi (310 kPa). Gradually increased. The vacuum bag was then vented to release the vacuum and the temperature was increased to 350 ° F. (177 ° C.) at 5 ° F./min (2.8 ° C./min) and maintained for 1 hour. The cured and bonded test sample is then cooled to room temperature at 10 ° F./min (5.5 ° C./min), at which point the pressure is released and the cured article is removed from the autoclave and vacuum bag. Removed from.

Abbreviations used Solvents and other reagents used were obtained from Sigma-Aldrich Chemical Company (Milwaukee, Wis.) Unless otherwise specified.
BZ-1-Araldite 35600 resin, bisphenol A-benzoxazine (Huntsman Advanced Materials America Inc. (The Woodlands TX))
BZ-2-Handbook of Benzoxazine Resins, Elsevier, 2011, p. Diphenyl-Jeffamine D400 benzoxazine prepared according to the procedure described in 212. BZ-3-Handbook of Benzoxazine Resins, Elsevier, 2011, p. P-cresylbenzoxazine of aniline prepared according to the procedure described in 212. HOTBN-hydroxyl-terminated partially epoxidized oligo (butadiene) (Sigma-Aldrich, Milwaukee, WI)
ATBN-amine-terminated oligo (butadiene-acrylonitrile) (Emerald Performance Materials, Akron OH)
Fumed silica-CAB-O-SIL TS-720 fumed silica (Cabot Corporation, Billerica MA)
· SeS ₂ - selenium disulfide (Sigma-Aldrich)
・ Se-Selenium (Alrich)
Nitrile rubber-Nipol 1000x88 (Zeon Chemicals, LP; Louisville, KY)
・ Zinc oxide-Kadox 930C Zinc Oxide (Horsehead Corporation, Monaca, PA)
Curing agent—Santacure CBS, N-cyclohexyl-2-benzothiazole sulfenamide (Flexsys America LP; Akron OH)
Sulfur-ACROCHEM Microfine Wettable MC Sulfur, elemental sulfur (Acrochem Corp. Akron, OH)
・ Phenolic resin-Durez 5980 phenolic resin (Durez Corporation, Addison, TX)
MEK-methyl ethyl ketone (EMD Chemicals, Inc. (Gibbtown, NJ)
MPK / MIBK-methyl isopropyl ketone (Eastman Chemical Company, Kingsport, TN)
Toluene-EMD Chemicals, Inc. (Gibbown, NJ)
Deuterated chloroform containing deuterated chloroform-TMS (tetramethylsilane) (Cambridge Isotopes, Andover, MA)
Release liner-Product No. 23210, 76 # BL KFT H / HP 4D / 6MH (Loparex, Iowa City, IA)
TMMP-trimethylolpropane tris (3-mercaptopropionate) (Wako Chemical USA, Inc. (Richmond, VA)

Example 1
Finely pulverized powders of BZ-1 (23.1) and sulfur (3.2 grams) were mixed in an equimolar ratio and stirred and shaken for about 1 minute with a Wig-L-Bug shaker. Approximately 15.4 milligrams (mg) of the mixture was heated to 320 ° C. with DSC (Seiko) as described above. The DSC trace showed an exotherm with a high temperature peak of approximately 211 ° C., a cure start temperature of approximately 140 ° C., and the total energy released during the cure of 221 J / gram. The trace further showed a small and sharp exotherm with a peak at approximately 113 ° C., which is consistent with the reported melting point of sulfur.

(Example 2)
BZ-2 (33.3 grams) and finely ground sulfur (3.2 grams) were mixed in an equimolar ratio and stirred vigorously for approximately 1 minute. Approximately 20.3 mg of the mixture was heated to 320 ° C. with DSC as described in Example 1. The DSC trace showed an exotherm with double hot peaks at about 170 ° C. and 225 ° C. and a cure onset temperature of about 130 ° C. The total energy released during curing was 221 J / gram. The trace further showed a small and sharp exotherm with a peak at approximately 113 ° C., which is consistent with the reported melting point of sulfur.

Comparative Examples C1-C2
Approximately 4.4 mg of BZ-1 (C1) and approximately 12.0 mg of BZ-2 (C2) were heated to 320 ° C. with DSC as described in Example 1. Each DSC trace showed peak exotherm temperatures of 240 ° C. and 246 ° C., cure onset temperatures of 190 ° C. and 190 ° C., and energy released during cure of 323 and 113 J / g for C1 and C2, respectively.

Examples 3-8 and Comparative Example C1A
BZ-1 and sulfur finely divided powders of various molar ratios (BZ: S ratio) from 10X to 1: 1 as shown in Table 1 were prepared as described in Example 1. Each amount is also shown in grams. The approximate amount of each mixture shown in the table was heated to 300 ° C. with DSC (TA).

  Example C1A was Example C1 tested on TA DSC simultaneously with Examples 3-8. The results from the DSC trace for peak exotherm temperature (peak), cure start temperature (start), and total energy released during cure (energy) are shown in Table 1 and FIG.

(Examples 9 to 11)
Molten BZ-3 (2.24 g, 0.01 mol) at 30 ° C. is mixed with sulfur (0.16 g, 0.005 mol) and the mixture is allowed to react at 170 ° C. for 1 hour, followed by 150 ° C. for 14 hours. And then cooled to room temperature.

  Example 10 was prepared according to the same procedure except that 30 ° C. molten BZ-1 (2.31 g, 0.01 mol) and sulfur (0.032 g, 0.01 mol) were used.

  Example 11 mixes molten 30 ° C. BZ-3 (2.24 g, 0.01 mol) with sulfur (0.32 g, 0.01 mol) and reacts the mixture at 200 ° C. for 1 minute, then at room temperature. It was prepared by cooling to.

Solutions of each of the reaction products of Examples 9-11 were prepared by dissolving the cooled product in deuterated chloroform at a concentration of 0.3 grams per liter (g / L). The solution was used to measure ³ C and ¹ H NMR spectra.

  The 1: 1 molar ratio composition broadened the cure exotherm peak with a dramatic decrease in the energy released therein, in addition to the sulfur catalysis in the ring opening of benzoxazine, It means that the phenomenon occurred. When a similar composition was analyzed by proton NMR with a short reaction time (eg, 1 minute at 200 ° C.), peaks consistent with the oxazine proton (2 at 5.3 ppm and 2 at 4.6) were halved in intensity. However, only a quarter of the possible ring-opening polymer products were observed in the 3.5-4.5 ppm region. At the same time, a considerable amount of formaldehyde formation (8.5 ppm) is observed, but formaldehyde is the expected product of benzoxazine ring decomposition. In these compositions, sulfur appeared to tend to decompose as much as it polymerizes the benzoxazine ring.

  When the ratio of sulfur to benzoxazine was reduced and the reaction proceeded under milder conditions, most of the oxazine protons were converted to ring-opened polymer structures. Furthermore, the numerous peaks and their broadening due to the same structural mechanism means that the products are not dimers in nature, but rather oligomers and polymers.

(Examples 12 to 18)
The finely pulverized powders of BZ-1 and selenium disulfide having the molar ratios and amounts shown in Table 3 were mixed together and then stirred and shaken for about 1 minute with a Wig-L-Bug shaker. Each mixture in the approximate amount (DSC amount) in the table was heated to 300 ° C. with DSC (TA). Data from the DSC trace are shown in Tables 2 and 3.

(Examples 19 to 20)
The amounts of BZ-1 and selenium finely ground powder shown in Table 3 were mixed as described in Example 12. An approximate amount (DSC amount) of each mixture was heated to 320 ° C. with DSC (TA). The results of the DSC trace are shown in Table 3 and FIG.

  The peak exotherm temperature (peak), cure start temperature (start), and energy released during cure (energy) are shown in Table 4 to illustrate the effect of the catalyst on compositions having various BZ-1: catalyst ratios. explain.

(Examples 21 to 22)
In Example 21, a mixture of 2.24 grams (0.01 mol) of BZ-3 and 0.014 g (0.0001 mol) of SeS ₂ was heated in an oven at 150 ° C. for 2 hours and then allowed to cool to room temperature. It was.

  In Example 22, a mixture of 2.24 grams (0.01 mol) BZ-3 and 0.008 g (0.0001 mol) Se was heated in an oven set at 220 ° C. for 2 hours, then to room temperature. Allow to cool.

Each reaction product was dissolved in deuterated chloroform. For each composition, ⁷⁷ Se NMR data was collected from the NMR spectrometer. The data showed only a baseline, which means that selenium was not incorporated into the polymer chain and acted as a catalyst.

Examples 23-24, Comparative Example C3
The composition shown in Table 5 contains ground nitrile rubber and curable resin (BZ-1 or phenol) in a 16 ounce glass bottle and then a solvent (MEK, MPK / MIBK, And toluene). The glass bottle was placed on a roller mixer and mixed continuously throughout the night. After the rubber and resin were completely dissolved, powder (sulfur, zinc oxide, and hardener) was added and dispersed using a high speed dispersion mixer for approximately 15 minutes. The resulting mixture was knife coated to a wet thickness of about 254 micrometers (10 mils) on a release coated paper liner. The coated adhesive was allowed to dry overnight at room temperature (75 ° F. (24 ° C.)) and then in an oven set at 180 ° F. (82 ° C.) for 30 minutes. The thickness of the dried adhesive film was approximately 152 micrometers (6 mils) and the adhesive was tested at 24 ° C. according to the overlap shear strength procedure described above. The results are shown in Table 6.

(Examples 25-26)
Two molten solutions were prepared by heating BZ-1 (23.1 grams, 0.1 mol) and sulfur (0.1 g) to 100 ° C. HOTBN (7 g and 2 g) was then heated to 100 ° C. and added to each molten BZ-1 / sulfur solution to form 23% and 8% HOTBN compositions for Examples 25 and 26, respectively. While hot, the composition was stirred into a homogeneous mass at 3000 rpm for 30 seconds using a high speed shear mixer (DAC Speed Mixer, Model 400-FVZ). The hot mixture was used to prepare the samples for dynamic mechanical analysis described above. The DMA trace shows a wide viscoelastic region, which indicates that the cured composition is useful as a hard thermoset adhesive and vibration damping composition.

(Examples 27 to 28)
While hot, the compositions of Examples 25 and 26 were coated with a knife coating set at 100 ° C. between two silicone release-coated PET liners to a thickness of about 27 for each of Examples 27-28. The knife coater on which a 125 micrometer film was formed was set at 100 ° C. The films were tested for overlap shear (OLS) and floating roller release (FRP) according to the test methods described above. The test results are shown in Table 7.

(Examples 29 to 30)
A finely ground powder of BZ-1 (1 g, 0.0044 mol) and sulfur (0.01 g) was vigorously stirred. Then 1 gram of HOTBN was added and hand stirred using a spatula to a homogeneous mass. Approximately 17.54 mg of the mixture was used for DSC analysis.
Example 30 was prepared in the same manner except that 0.5 g HOTBN was added instead of 1 g, and approximately 13.51 mg was used for DSC analysis.
The DSC results are shown in Table 8 and compared with Example 3 without HOTBN.

(Examples 31-33)
For Examples 31-33, finely pulverized powders of BZ-1 (1 g, 0.0044 mol) and sulfur (0.01 g) were combined and vigorously stirred. ATBN was added to each example in amounts of 0.275 g, 0.5 g, and 1.0 g, respectively, and stirred manually using a spatula to form a homogeneous mass. Approximately 13.51 mg from each example was used for DSC analysis and the results are shown in Table 9. The traces of Examples 31-33 showed two peaks, one at low temperature. The lower temperature indicates onset, peak, and energy released during amine cure from ATBN with benzoxazine. Sulfur cure had higher temperature and energy release.

(Examples 34 to 40)
The composition was prepared by heating ATBN to 100 ° C. and adding it to the molten solution of BZ-1 and sulfur in the amounts shown in Table 10. Silica (Cab-O-Sil) was then added and the mixture was stirred into a homogeneous mass for 30 seconds at 3000 rpm using a high speed shear mixer (DAC) while hot.

  While hot, test coupons for DMA testing were prepared using some of the compositions of Examples 34, 35, 39, and 40. Data from DMA scans indicate that ATBN rubber remains miscible with benzoxazine over a wide range of compositions and thermal cycles. Morphological properties indicate that the compatibility of ATBN and benzoxazine has resulted in high glass transition temperatures over a wide range of temperatures, which is a hard, high modulus composition with excellent thermal stability It is the feature.

  The remainder of each composition of Examples 34-38, while hot, was coated between two silicone release coated PET films using a knife coater set at 100 ° C. to a thickness of 125 micrometers. The film was formed. The film was allowed to cool to room temperature and then used to prepare a test sample for overlap shear and floating roller peel adhesion as described above.

  Test samples for overlap shear and floating roller peeling were prepared from the coated adhesive films of Examples 34-36. The test sample was cured for 2 hours in an oven set at 180 ° C.

  Test samples for overlap shear prepared from the coated films of Examples 37-38 were cured in an autoclave at 150 ° C. for 2 hours and then tested as in Examples 34-36. Table 11 shows the overlap shear test results, and Table 12 shows the floating roller peeling test results.

−−試験されず

-Not tested

  Samples for the overlap shear test of Examples 37-39 were also cured in an oven at 180 ° C. for 2 hours and allowed to cool to room temperature. Samples were stored at room temperature until tested at room temperature and 136 ° C. After annealing the sample for 1 week at 177 ° C., a third set of samples was tested at 177 ° C. The test results are shown in Table 13.

  About 5-10 g of sample was used to perform thermogravimetric analysis in air as described above to determine the thermal stability of the composition of Example 39. The activation energy of Example 39 shown in Table 14 was measured using an Arrhenius plot. For comparison purposes, Examples C4 (homopolymerized BZ-1) and C5 (BMP-1 cured with TMMP) were similarly tested. The compositions were polymerized as in co-pending US Patent Application Nos. 2010/0312004 and 2010/0307680 (Gorodishaer et al.).

  The data in Table 14 indicates that higher activation energy is required for pyrolysis of the composition of the present invention, and therefore the thermal stability of the composition of the present invention is superior.

(Example 41)
A molten composition was prepared according to the procedures described in Examples 25-26 except for BZ-1 (138.6 grams, 0.6 mol) sulfur (0.78 g) and ATBN (18 g). The high temperature composition was poured into a heated mold and the shrinkage after curing described above was measured. The shrinkage of the polymerized composition was 0.83%.

(Examples 42 to 46)
By thoroughly mixing together the finely pulverized powder of BZ-1 (23.1 grams, 0.1 mol) and the amount of tetraphosphorus trisulfide (P ₄ S ₃ ) powder shown in Table 14, the composition Was prepared. Samples (3-10 mg) were each heated to 330 ° C. at 10 ° C./min with DSC. The results from the DSC trace of peak exotherm temperature, onset of cure temperature, and energy released during cure are shown in Table 15.

Table 16 shows the catalytic effects of the _two sulfide catalysts (P ₄ S ₃ and SeS ₂ ).

［式中、各Ｒ^１は、Ｈ又はアルキル基であって、脂肪族アルデヒドの残基であり、
Ｒ^２は、Ｈ、共有結合、又は多価（ヘテロ）ヒドロカルビル基、好ましくは、Ｈ、共有結合、又は二価アルキル基であり、
Ｒ^５は、一級アミノ化合物Ｒ^５（ＮＨ_２）_ｍ（式中、ｍは、１〜４である）の（ヘテロ）ヒドロカルビル残基であり、
ｙ＋ｚは、少なくとも２である］、で表される１つ以上のポリマーと、
前記触媒の残基と、を含む、実施形態１〜１７のいずれか１つに記載の重合性組成物。
１９．Ｒ^５が、ポリ（アルキレンオキシ）基である、実施形態１８に記載の重合性組成物。
２０．Ｒ^５が、アリール基と脂肪族基との混合物を含む、実施形態１８に記載の重合性組成物。
２１．反応性希釈剤を更に含む、実施形態１〜２０のいずれか１つに記載の重合性組成物
２２．前記反応性希釈剤が、式：
Ｒ^８−（ＺＨ）_ｐのものである、実施形態２１に記載の重合性組成物。
［式中、Ｒ^８は、（ヘテロ）ヒドロカルビル基であり、
Ｚは、−Ｓ−又は−ＮＲ^９（式中、各Ｒ^９は、Ｈ又はヒドロカルビル基である）の混合物であり、
ｐは、１〜６である］
２３．化合物Ｒ^８−（ＺＨ）_ｐからのアミン基及び／又はチオール基の合計と、ベンゾオキサジン基と、の比が、約３：１〜１００：１である、実施形態２２に記載の重合性組成物。
２４．フィルム形成ポリマー又はオリゴマーを更に含む、実施形態１〜２３のいずれか１つに記載の重合性組成物。
２５．前記フィルム形成ポリマーが、前記ベンゾオキサジンに対して１〜７５重量％の量である、実施形態２４に記載の重合性組成物。
２６．エポキシ樹脂を更に含む、実施形態１〜２５のいずれか１つに記載の重合性組成物。
The present disclosure provides the following representative embodiments.
1.
a) benzoxazine;
b) a polymerizable composition comprising elemental sulfur, elemental selenium, and a catalyst selected from sulfides or selenides of Group V elements or Group VI elements.
2. The polymerizable composition of embodiment 1 comprising from 0.1 to 10 mole percent of the catalyst.
3. The polymerizable composition of embodiment 1 or 2, further comprising a toughening agent.
4). The polymerizable composition according to any of embodiments 1-3, wherein the toughening agent is present at about 3% to 35% by weight of the benzoxazine.
5. The polymerizable composition according to any one of Embodiments 1 to 4, wherein the reinforcing agent is a polymer compound having both a rubber phase and a thermoplastic phase.
6). The toughening agent is a grafted polymer having a polymerized diene rubbery core and a shell grafted with an acrylic ester, methacrylic ester, monovinyl aromatic hydrocarbon, or a mixture thereof; The polymerizable composition according to Embodiment 5.
7). The polymerizable composition according to embodiment 6, wherein the rubbery core includes polymerized butadiene or a mixture of butadiene and styrene.
8). The polymerizable composition according to embodiment 6, wherein the shell comprises a methacrylic ester.
9. The polymerizable composition according to embodiment 8, wherein the methacrylic acid ester comprises a lower alkyl-substituted methacrylate.
10. The polymerizable composition of embodiment 6, wherein the shell comprises a monovinyl aromatic hydrocarbon.
11. The polymerization according to embodiment 10, wherein the monovinyl aromatic hydrocarbon is selected from styrene, α-methylstyrene, vinyltoluene, vinylxylene, ethylvinylbenzene, isopropylstyrene, chlorostyrene, dichlorostyrene, and ethylchlorostyrene. Sex composition.
12 The toughening agent is a core-shell polymer, the core being a rubbery polyacrylate polymer having a glass transition temperature of less than about 0 ° C., the shell grafted to the core, and greater than about 25 ° C. The polymerizable composition of embodiment 6, which is a thermoplastic polyacrylate polymer having a glass transition temperature of
13. The polymerizable composition of embodiment 12, wherein the core is selected from polybutyl acrylate and polyisooctyl acrylate and the shell is polymethyl methacrylate.
14 Said reinforcing agent is in the free-radically polymerizable monomers polymerizable composition is a mixture polymerized with a polymer stabilizer that is soluble, and an elastomeric particles having a T _g of less than about 25 ° C., the embodiment 6 The polymerizable composition as described.
15. Embodiment 15. The polymerizable composition according to any one of embodiments 1-14, wherein the toughening agent comprises a nucleophilic reactive group that opens a portion of the benzoxazine.
16. Embodiment 16. The polymerizable composition according to any one of embodiments 1-15, comprising a mixture of benzoxazines derived from both aliphatic amines and arylamines.
17. The polymerizable composition according to any one of embodiments 1-16, comprising a benzoxazine derived from poly (alkyleneoxy) diamine.
18. formula:

Wherein each R ¹ is H or an alkyl group and is a residue of an aliphatic aldehyde;
R ² is H, a covalent bond, or a polyvalent (hetero) hydrocarbyl group, preferably H, a covalent bond, or a divalent alkyl group;
R ⁵ is a (hetero) hydrocarbyl residue of the primary amino compound R ⁵ (NH ₂ ) _m , where m is 1-4.
y + z is at least 2], and one or more polymers represented by:
The polymerizable composition according to any one of Embodiments 1 to 17, comprising a residue of the catalyst.
19. The polymerizable composition according to embodiment 18, wherein R ⁵ is a poly (alkyleneoxy) group.
20. R ⁵ comprises a mixture of an aryl group and an aliphatic group, polymerizable composition according to embodiment 18.
21. 21. The polymerizable composition according to any one of embodiments 1-20, further comprising a reactive diluent. The reactive diluent has the formula:
R ⁸ - _(ZH) is of _p, the polymerizable composition of embodiment 21.
[Wherein R ⁸ is a (hetero) hydrocarbyl group;
Z is a mixture of —S— or —NR ^{9 where} each R ⁹ is H or a hydrocarbyl group;
p is 1-6]
23. Compound ^R 8 - _(ZH) sum of the amine groups and / or thiol groups from _p, and benzoxazine groups, the ratio of about 3: 1 to 100: 1, the polymerizable composition of embodiment 22 object.
24. Embodiment 24. The polymerizable composition according to any one of embodiments 1-23, further comprising a film-forming polymer or oligomer.
25. Embodiment 25. The polymerizable composition of embodiment 24, wherein the film-forming polymer is in an amount of 1 to 75% by weight relative to the benzoxazine.
26. The polymerizable composition according to any one of embodiments 1 to 25, further comprising an epoxy resin.

Claims (13)

a) benzoxazine;
b) A polymerizable composition comprising elemental sulfur, elemental selenium, phosphorus sulfide, sulfur selenide, and a catalyst selected from selenium sulfide. The polymerizable composition of claim 1 comprising 0.1 to 10 mole percent of the catalyst relative to the benzoxazine .   The polymerizable composition of claim 1 further comprising a toughening agent.   The polymerizable composition of claim 3, wherein the toughener is present at 3% to 35% by weight of the benzoxazine.   The polymerizable composition of claim 1 comprising a mixture of benzoxazines derived from both aliphatic and arylamines.   The polymerizable composition of claim 1 comprising benzoxazine derived from poly (alkyleneoxy) diamine. After polymerization, the formula:

Wherein each ^{R 1} is H or an alkyl group,
R ² is H,,
R ⁵ is alkyl, cycloalkyl, or aryl ;
m is 1 to 4,
y + z is at least 2]
One or more polymers represented by:
The polymerizable composition according to claim 1, comprising a residue of the catalyst. The polymerizable composition according to claim 7, wherein R ⁵ is a poly (alkyleneoxy) group. The polymerizable composition according to claim 7, wherein R ⁵ comprises a mixture of an aryl group and an aliphatic group. Further comprising a reactive diluent;
The polymerizable composition of claim 1, wherein the reactive diluent is of the formula: R ⁸ — (ZH) _p .
[Wherein R ⁸ is a (hetero) hydrocarbyl group;
Z is a mixture of —S— or —NR ^{9 where} each R ⁹ is H or a hydrocarbyl group;
p is 1-6] The compound ^R 8 - the sum of _(ZH) amine and / or thiol groups from _p, the ratio of the benzoxazine groups, 3: 1 to 100: 1, the polymerizable composition of claim 10 object.   The polymerizable composition of claim 1, further comprising a film-forming polymer or oligomer in an amount of 1 to 75% by weight relative to the benzoxazine.   The polymerizable composition according to claim 1, further comprising an epoxy resin.

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